Treatment of textiles and composition useful therefor



Patented Feb. 29, 1944 UNITED STATES PATENT OFFICE TREATMENT OF TEXTILESAND COMPOSI- TION USEFUL THEREFOR Joseph Edward Smith, Wilmington, Del,assignor to E. I. du Pont de Nemours & Company, Wilmington, DeL, acorporation of Delaware No Drawing. Application August 3, 1940, SerialNo. 351,083

Claims. (cl. 260-32) fibers and nylon. A further object is thepreparation of resin dispersions useful for finishing textile fabricswhich are substantive to animal fibers and nylon. Other objects willappear hereinafter.

These objects are accomplished by the following invention. A solution inwater of a partially saponified polyvinyl acetate more particularly ofthe type described in copending application Serial No. 351,082, filed ofeven date herewith is agitated vigorously with an ester of methacrylicacid or vinyl alcohol ester containing a small amount of benzoylperoxide. During agitation a positive charge is obtained on the emulsionparticle by incorporating a water soluble polyvalent metal salt or aheavy metal salt. The emulsion is heated to produce polymerization ofthe methacrylic acid ester or vinyl alcohol ester and form a stabledispersion of the resin. The dispersion is substantive from a diluteaqueous dispersion to animal fibers, including wool and silk, and tonylon. As an a1- ternative, the heavy metal salt or multivalent metalsalt ay be added to the polymerized resin dispersion to obtain apositively charged dispersion substantive to animal fibers and to nylon.

Aqueous dispersions of polymeric esters of methacrylic acid and vinylalcohol can be prepared by emulsion polymerization. Emulsifylng anddispersing agents which may be used for this purpose include typicalanionic surface active agents, as alkyl naphthalene sulfonic acid saltsand fatty alcohol sulfates, as well as protective colloids, such asnatural gums, starches and gelatin. Dispersions thus prepared are, bythe nature of the colloidal system, negatively charged and haveinsufficient substantivity for animal fibers and nylon to be applied bya process of exhaustion from a dilute bath under practical conditions.Such dispersions have to be applied by dipping the fabrics to be treatedin a bath followed by extraction of excess liquor from the surface ofthe fabrics and drying. The amount of resin absorbed by the fabric insuch a process is directly proportional to the amount of liquor retainedby the fabric from the bath.

It frequently is advantageous to apply resin ization of the emulsifiedmonomer.

dispersions to textile materials by a process of exhaustion from thebath onto the fibers in order to obtain economical use of the resin.This is particularly true in establishments which process goods thatcannot conveniently be treated on the quetsch, For example, it isdesirable in treating hosiery of nylon, wool or silk, as well as knittedgoods in general, to exhaust the resin dispersion from a long bath ontothe goods. In an application of this nature the greater part of theresin is entirely removed from the bath by the goods, regardless of theamount of water absorbed by the goods. Hence, in this process the amountof resin absorbed by the goods is directly proportional to the amount ofresin dispersed in the bath regardless of the bath volume.

In carrying out the invention, an aqueous solution of a partiallysaponified polyvinyl acetate is agitated vigorously with a monomericmethacrylic acid ester or vinyl alcohol ester containing a small amountof benzoyl peroxide. Aluminum acetate or barium chloride and acetic acidare added while continuing the agitation. A stable emulsion is obtained.The emulsion is heated to a temperature above C. to induce polymer- Thebenzoyl peroxide acts as an oxidation catalyst to promote thepolymerization of the monomer. The resin dispersions produced by thisinvention are stable. As an alternative, the polyvalent metal salts orheavy metal salts can be added to the resin dispersions followingpolymerization.

Partially saponified polyvinyl acetate is highly soluble in water, butis difflcult to dissolve rapidly since the material tends to form lumpssurrounded by a gelatinous film on contact with water. The gelatinousfilm retards the rate of penetration into the mass and it is necessaryto agitate for several days to obtain a solution. However, if the watercontains 1% of a surface active agent, as for example, technical dodecyldiethylcyclohexylamine sulfate, on the weight of the partiallysaponified polyvinyl acetate, a much more rapid rate of solution isobtained, particularly at elevated temperatures. A concentrated solutionof a polyvinyl alcohol derivative can be prepared in 30 minutes at F.with good agitation, provided the wetting agent is present. Theinclusion of a small amount of technical dodecyl diethylcyclohexylaminesulfate with the polyvinyl alcohol derivatives in the emulsion has nodetrimental effect on the ultimate stability of the dispersed product.It is advantageous to use a small amount of technical dodecyldiethylcyclohexylamine sulfate in the preparation of the emulsions toassist in dissolving the polyvinyl alcohol derivative.

It frequently is advantageous to use plasticizers with methacrylic acidester and vinyl alcohol ester polymers to obtain the desired effects.Satisfactory plasticizers are discussed by Strain, Kennelly, Dittmar,Ind. and Eng. Chem, 31, 382 (1939).

Plasticizers, which are particularly of value in the compositions ofthis invention, are di-(butoxy ethyl) phthalate, butyl phthalyl butylglycolate, and di(methylcyclohexyl) adipate.

The resin dispersions prepared according to this invention have thecommon property of bein po i ively charged as shown by movement of thedispersed particles from the positive to the negative pole in anelectric field. The resin particles are substantive to wool, silk andnylon and are absorbed from a dilute bath by fabrics made of thesematerials. The degree of substantivity for the different fibers variesconsiderably; the substantivity of the dispersed resin particles forwool, silk and nylon is a variable that is strongly influenced by the pHand temperature in the bath. Generally speaking, the substantivity isgreater the higher the temperature and pH in the bath. It has been foundin practice that the pH range most suitable for use in applying thedispersions to silk is 4.0 to'7.0; to wool, 4.5 to 7.0; and to nylon 4.8to 7.0. The dispersions have a high affinity for silk, wool or nylon inbaths more alkaline than 7.0 but the dispersions are in a metastablestate and frequently are absorbed so rapidly that the particles are notdeposited on the fibers uniformly. The dispersions have some affinityfor the fibers at pH values smaller than those given above, but the rateof absorption of the dispersion is frequently too slow to be practical.The dispersions are highly substantive to wool and silk at temperaturesas low as 75 F.; temperatures above 90 F. are frequently required forsatisfactory application to nylon.

The resin dispersions described herein may be used to advantage incombination with positively charged wax dispersions in the finishing ofwool, silk and nylon textiles and more particularly in the finishing ofhosiery. The combination of resin and wax dispersions is applied by thesame methods as described for the resin dispersions alone.

The following examples are illustrative of the invention but are notintended as limiting, it in any way. Parts are given by weight exceptwhere it is otherwise indicated.

ExArnLn 1 g parts of methyl methacrylate monomer containing 0.2 part ofbenzoyl peroxide were mixed with 2.0 parts of a partially saponifled Plyvinyl acetate, 0.02 part of technical dodecyl diethylcyclohexylaminesulfate, and 73.68 parts of water by means of a high speed mixer. Thesaponifi cation number of the partially saponifled polyvinyl acetate was109 and the viscosity of a 4% aqueous solution at 20 C. was 20 c. p. 3.8parts of a 32% basic aluminum acetate solution and 0.5 part of aceticacid were added while continuing the agitation. After agitating for atotal of 3 minutes, a stable emulsion was obtained. The emulsion washeated for 4 hours at 67 C. to obtains dispersion of a resinous polymer.The dispersion obtained was stable.

Emu: 2

1.0 gram of the product from Example 1 was dispersed in 200 cc. of softwater and the pH of the bath adjusted to 4.0 by the addition of aceticacid. The bath was placed in a pint Mason jar and a 10 gram strip ofsilk piece goods added to the jar. The bath was agitated for 10 minutesat F. and for 5 minutes at F. At least 80% of the resin disersion wasabsorbed by the silk from the bath. This was determined by comparison ofthe opacity of the exhausted bath with standard dispersions of knownconcentrations. The silk was hydro-extracted and dried at 200 F. toobtain a full, delustered fabric.

Similar results were obtained in applications from baths adjusted by theaddition of either acetic acid and/or ammonia to a pH of 5.0, 6.0 and6.6.

EXAMPLE 3 EXAMPLE 4 One gram of the product from Example 1 was dispersedin 200 cc. of soft water and the pH of the bath adjusted to 4.5. A tengram skein of wool yarn was entered in the bath at 100 F. and agitated.The dispersed phase was absorbed by the yarn in about 15 minutes. Theskein was hydro-extracted and dried at about 200 F. Considerablefullness was added to the yarn.

EXAMPLE 5 The monomer of n-butyl methacrylate was substituted for methylmethacrylate monomer in A stable resin dispersion was obtained.

The dispersed resin was applied to wool, silk and nylon as in Examples2, 3 and 4. Considerable fullness, body and stiffness were added to thetextiles.

EXAMPLE 6 Iso-butyl methacrylate was substituted for methyl methacrylatein Example 1. A stable resin dispersion was obtained.

The dispersed resin was applied to wool, silk and nylon as in Examples2, 3 and 4. Considerable fullness, body and stiffness were added to thetextiles.

Exnlru: 7

10 parts of methyl methacrylate monomer and 10 parts of n-butylmethacrylate monomer containing 0.2 part of benzoyl peroxide were mixedwith 2.0 parts of a partially saponified polyvinyl acetate, 0.02 part oftechnical dodecyl diethylcyclohexylamine sulfate, and 73.68 parts ofwater by means of a high speed mixer. The saponiflcation number of thepartially saponified poLvvinyl acetate was and the viscosity of a 4%aqueous solution at 20 C. was 20 c. p. 3.8 parts of a 32% basic aluminumacetate solution and 0.5 part of acetic acid were added while continuingthe agitation. After agitating for a total of 3 minutes, a stableemulsion was obtained. The emulsion was heated for four hours at 67 C.to obtain a dispersion of a resinous polymer. The dispersion obtainedwas stable to storage. The dispersed resin was substantive to silk, wooland nylon when applied under the conditions described in Examples 2, 3and 4. A full, crisp hand was acquired by the treated fabrics on dryingat 200 F.

EXAMPLE 8 15 parts of methyl methacrylate monomer and parts ofdi(methylcyclohexyl) adipate were substituted for the methylmethacrylate in Example 1. A stable dispersion of a polymerized resinwas obtained. The material was substantive to wool, silk and nylon asshown in application tests made under the conditions described inExamples 2, 3 and 4. The treated fibers acquired a fuller hand withoutgreatly increasing the stiffness. The finish on the nylon stockingimproved the resistance of the stocking to snagging. Thedi(methylcyclohexyl) adipate of this example may be replaced bydi(butoxy ethyl) phthalate, di-butyl phthalate, or butyl phthalyl butylglycolate.

The methyl methacrylate of the example may be substituted by n-butylmethacrylate or isobutyl methacrylate or by mixtures of the diner-- entmethacrylic acid esters. Finishes obtained from dispersions preparedwith these substitu tions for methyl methacrylate are fuller and crisperthan those prepared with methyl methacrylate.

EXAMPLE 9 Composition A Per cent Refined paramn wax 16.7 Acetate ofdeacetylated chitin 1.3 Basic aluminum acetate 3.0 Acetic i 0.5

Technical dodecyl diethylcyclohexylamine sulfate 0.09 Water 78.41

A 10 gram silk stocking was entered in the bath, contained in a pintMason jar, at 80 F. The pH of the bath was 5.5. The jar was agitated ina Launderometer for 10 minutes. About 80% of the. dispersion wasabsorbed by the stocking. The bath was heated to 100 F. and agitated foran additional 5 minutes. The dispersion was completely removed from thebath. The stocking was hydro-extracted and boarded on an electricallyheated drying form at about 220 F. The treated stocking was highlydelustered and water repellent. A soft hand and considerable fullnesswere added to the stocking. The finish was resistant to removal bylaundering.

(b) 1.0 gram of the composition from Example 5 and 0.5 gram ofComposition A were applied to a 10 gram silk stocking as in (a). Thetreated stocking was highly water repellent and the hand of the stockingwas considerably crisper and fuller "compared with the untreatedstocking. The finish was resistant to removal by laundermg.

(c) 0.3 gram of the composition from Example 1, 0.7 gram of thecomposition from Example 5 and 0.3 gram of Composition A were applied toa 10 gram silk stocking as in (a) The treated stocking was highlydelustered and water repellent and had a full hand. The finish wasresistant to laundering.

(d) 0.25 part of the composition from Example 5 and 0.25 part ofComposition A were dispersed in 199.5 parts water and applied to a woolserge fabric as in Example 4. The fabric was dried on a mangle at 220 F.The dried fabric had a full hand and was highly water repellent. Thefinish was resistant to removal by laundering.

(e) 0.7 gram of the composition containing nbutyl methacrylateplasticized with di(methylcyclohexyl) adipate from Example 8 and 0.3gram of Composition A were dispersed in 199 cc. of water and applied toa ten gram nylon stocking as in Example 3. A full, firm hand withconsiderable surface lubrication was obtained. The stocking was highlywater repellent. The finish was resistant to removal by laundering.

EXAMPLE 10 Twenty-five parts of vinyl acetate monomer containing 0.25part of benzoyl peroxide were mixed by high speed agitation with 70.70parts of an aqueous solution containing 2.5 parts of a partiallysaponified polyvinyl acetate (saponification No. 180; viscosity in a 4%aqueous solution at 20 C., 40 c. p.) and 0.025 part of technical dodecyldiethylcyclohexylamine sulfate. 3.8 parts of a 32% basic aluminumacetate solution and 0.5 part of glacial acetic acid were added whilecontinuing the agitation. After agitating for a total of 3 minutes, astable emulsion was obtained. The emulsion was heated for 6 hours at 67C. to obtain a stable dispersion of a resinous polymer.

EXAMPLE 1 l 6.25 parts of vinyl acetate monomer and 18.75 parts ofmethyl methacrylate monomer were substituted for the 25 parts of vinylacetate monomer in Example 10. The partically saponified polyvinylacetate used had a saponification number of 108 and a viscosity of 20 c.p. for a 4% solution at 20 C. A stable dispersion of a resinous polymerwas obtained.

EXAMPLE 12 20 parts of vinyl acetate monomer and 5 parts ofdi(butoxy-ethyl) phthalate were substituted for the 25 parts of vinylacetate monomer in Example 10. A stable dispersion of a resinous polymerwas obtained.

EXAMPLE 13 5 parts of vinyl acetate monomer, 15 parts of methylmethacrylate monomer and 5 parts of di- (butoxy-ethyl) phthalate weresubstituted for the monomers in Example 11. A stable dispersion of aresinous polymer was obtained.

EXAMPLE 14 EXAMPLE 15 One gram of the composition from Example 13 wasapplied to a 10 gram nylon stocking as in Example 3. A full, firm handwas obtained and the stocking was markedly improved in snag resistance.The finish was highly resistant to laundering.

EXAMPLE 16 One gram of the composition from Example 11 was applied to agram silk stocking as in Example 2. The stocking was boarded at 220 F.on a hoisery form. A full, firm hand was obtained. The finish was highlyresistant to laundering.

Exlmru: 17

One gram of the composition from Example 12 was applied to a 10 gramsilk stocking as in Example 2. The stocking was boarded on a hosieryform at 220 F. A full, crisp hand was obtained. The finish was highlyresistant to laundering.

Exsurtr: 18

The aluminum acetate of Example 1 was replaced by an equal weight ofbarium chloride. A\stable dispersion was obtained. Similar results wereobtained on applying the product to wool, silk and nylon as in Examples2, 3 and 4.

Exam 19 The aluminum acetate and acetic acid of Example 1 were replacedby equal weights of aluminum formats and formic acid. A dispersion wasobtained. Similar results were obtained on applying the product to wool,silk, and nylon as in Examples 2, 3, and 4.

The processes for preparing positively charged dispersions substantiveto silk, wool, and nylon described in this invention are applicable notonly to the methacrylates and vinyl acetate but to polymerizable waterinsoluble hydrocarbon derivatives and particularly to vinylidenecompounds. Typical vinylidene compounds are styrene, butadiene viny1chloride, vinyl acetate. acrylates, methacrylates, acrylonitriles,acrylamides, methacrylonitriles and methacrylamides. The vinylidenecompounds may be used separately or as mixtures to form interpolymers.The resinous polymers may be plasticized; typical plasticizers aredescribed by Strain, Kennelly, and Dittmar, Ind. Eng. Chem. 31, 382,1939.

The positive charge on the dispersed particles may be obtained by theaddition of water soluble heavy metal or multivalent salts instead ofaluminum acetate to the emulsions. For example. salts of Ba, Cd, Co, Fe,Ni, Mn, Zn, Sn, Pb, Sb, Bi, and Cr can be used. Formic, propionic,hydrochloric, sulfuric and other acids may be used to replace aceticacid in the emulsions. It is preferable to add the heavy metal saltsduring the process of emulsification; however, satisfactory substantiveemulsions can be obtained by adding the heavy metal salts or salts ofmultivalent metals to the aged dispersions.

Other substantially non-polar high molecular weight water-solubleprotective colloids may be used in place or partially saponifiedpolyvinyl acetate. In place of partially saponifled polyvinyl acetatethere may be used cellulose derivatives such as water-soluble methylcellulose, the ethylene oxide reaction product of oleyl alcohol, etc.

Compositions described herein are useful in the treatment of silkhosiery. When products of the invention are applied to nylon hosiery,knit goods and flat goods good bodying effects are obtained.

stable 1 to those specified in the subjoined claims, which Productscovered by the invention may be applied with positively chargedsubstantive wax dispersions, and combinations of the products with waxemulsions impart excellent bodying and water-repellent properties towool fabrics.

The primary advantages of the invention are the economical and uniformtreatment of silk, wool, and nylon textile materials with resinfinishes. The compositions described are particularly adapted to thetreatment of knitted fabrics which cannot be handled satisfactorily onthe quetsch.

Resin dispersions described herein when applied alone or with positivelycharged substantive wax dispersions produce finishes on silk hosierythat greatly improve the appearance and durability of the stockings. Thefinishes are much more durable and faster to washing than th finisheswhich have been previously used.

(1) Excellent delustering is obtained which is effective for the life ofthe stocking. The delustering is not characterized by the chalkinessobtained with opaque pigment delustrants.

(2) The application of a resin dispersion with a positively chargedsubstantive wax dispersion produces a water repellent, spot resistantfinish that is more durable than the effect obtained from the wax finishalone.

(3) The stockings show a regularity of stitch that is improved incomparison with untreated stockings. The treated stockings are moresheer in appearance.

(4) The resin dispersions or combination resin and positively chargedsubstantive wax dispersions applied as described in this inventionproduce a more uniform, reproducible finish. The fact that the finish iscompletely exhausted from the bath makes it possible to obtain the sameamount of finish on stockings from batch to batch, regardless of thesize of the batch and the ratio of bath to goods. The regulatedexhaustion of the finish makes possible the uniform application over thesurface of the stockings throughout the batch.

(5) The resin finish improves the resistance of the stocking tosnagging.

(6) The application of a resin finish with a positively chargedsubstantive wax dispersion produces stockings that board andhandle moreeasily than stockings finished with the finishes previously used.

(7) The application of the resin dispersions alone or in combinationwith positively charged (8) The application of the resin dispersionswith positively charged substantive wax dispersions makes it possible toobtain an economical,

uniform and reproducible water repellent and bodying effect on woolfabrics.

The subjoined claims are intended to cover not only the productsdescribed herein but to generically cover certain products which aredescribed and specifically claimed in my copending applications, SerialNumbers 351,084, 351,086, 351,087, and 351,088, filed on this same day.to which reference may be made for further disclosure. The resindispersions described and specifically claimed in the aforesaidcopending applications contain other ingredients, in addition modify theproperties of the resin dispersions or change the finishing effectswhich these dispersions impart to fabrics.

The above description and examples are intended to be illustrative onlyand not to limit the scope of the invention. Any departure therefromwhich conforms to the spirit of the invention is intended to be includedwithin the scope of the appended claims.

I claim: a

1. A substantive textile finishing composition adapted for applicationto textile fibers by a process of exhaustion from a dilute aqueous bathcomprisinga stable aqueous dispersion of a poly merized vinylidenecompound containing as the dispersing agent a substantially non-polarhigh molecular weight water soluble protective colloid of the groupconsisting of partially saponified polyvinyl esters, water solublemethyl celluloses and the water soluble ethylene oxide reaction productof oleyl alcohol, and containing as an agent which renders the dispersedpolymerized vinyl compound substantive to textile fibers. a watersoluble salt of a multivalent metal.

2. A substantive textile finishing composition adapted for applicationto textile fibers by a process of exhaustion from a dilute aqueous bathcomprising a stable aqueous dispersion of a polymerized vinyl acetatecontaining as the dispersing agent a su fitantially non-polar highmolecular weight water soluble protective colloid of the groupconsisting of partially saponified polyvinyl esters, water solublemethyl celluloses and the water soluble ethylene oxide reaction productof oleyl alcohol, and containing as an agent which renders the dispersedpolymerized vinyl acetate substantive to textile fibers, a water solublesalt of a multivalent metal.

3. A substantive textile finishing composition adapted for applicationto textile fibers by a process of exhaustion from a dilute aqueous bathcomprising a stable aqueous dispersion of a polymerized alkylmethacrylate containing as the dispersing agent a substantiallynon-polar high molecular weight water soluble protective colloid of thegroup consisting of partially saponified polyvinyl esters, water solublemethyl celluloses and the water soluble ethylene oxide reaction productof oleyl alcohol, and containing as an agent which renders the dispersedpolymerized alkyl methacrylate substantive to textile fibers a watersoluble salt of a multivalent metal.

4. A substantive textile finishing composition adapted for applicationto textile fibers by a process of exhaustion from a dilute aqueous bathcomprising a stable aqueous dispersion of a polymerized methylmethacrylate containing as the dispersing agent a substantiallynon-polar high molecular weight water soluble protective colloid of thegroup consisting of partially saponified polyvinyl esters, water solublemethyl celluloses and the water soluble ethylene oxide reaction productof oleyl alcohol, and containing as an agent which renders the dispersedpolymerized methyl methacrylate substantive to textile fibers a watersoluble salt of a multivalent metal.

5. A substantive textile finishing composition adapted for applicationto textile fibers by a process of exhaustion from a dilute aqueous bathcomprising a stable aqueous dispersion of a polymerized butylmethacrylate containing as the dispersing agent a substantiallynon-polar high molecular weight water soluble protective colloid of thegroup consisting of partially saponified polyvinyl esters, water solublemethyl celluloses and the water soluble ethylene oxide reaction productof oleyl alcohol, and containing as an agent which renders the dispersedpolymerized butyl methacrylate substantive to textile fibers a .watersoluble salt or a multivalent metal.

6. A substantive textile finishing composition adapted for applicationto textile fibers by a process of exhaustion from a dilute aqueous bathcomprising a stable aqueous dispersion of a polymerized vinylidenecompound containing as the dispersing agent a partially saponifiedpolyvinyl acetate, and containing as an agent which renders thedispersed polymerized vinyl compound substantive to textile fibers awater soluble salt of a multivalent metal.

7. A substantive textile finishing composition adapted for applicationto textile fibers by a process of exhaustion from a dilute aqueous bathcomprising a stable aqueous dispersion of a polymerized vinyl acetatecontaining as the dispersing agent a partially saponified polyvinylacetate, and containing as an agent which renders the dispersedpolymerized vinyl acetate substantive to textile fibers a water solublesalt of a multivalent metal.

8. A substantive textile finishing composition adapted for applicationto textile fibers by a process of exhaustion from a dilute aqueous bathcomprising a stable aqueous dispersion of a polymerized alkylmethacrylate containing as the dispersing agent a partially saponifiedpolyvinyl acetate, and containing as an agent which renders thedispersed polymerized alkyl methacrylate substantive to textile fibers awater soluble salt of a multivalent metal.

9. A substantive textile finishing composition adapted for applicationto textile fibers by a process of exhaustioi from a dilute aqueous bathcomprising-a stable aqueous dispersion of a polymer-' ized methylmethacrylate containing as the dispersing agent a partially saponifiedpolyvinyl acetate,.and containing as an agent which renders thedispersed polymerized methyl methacrylate substantive to textile fibersa water soluble salt of a multivalent metal.

10. A substantive textile finishing composition adapted for applicationto textile fibers by a process of exhaustion from a dilute aqueous bathcomprising a stable aqueous dispersion of a polymerized butylmethacrylate containing as the dispersing agent a partially saponifiedpolyvinyl acetate and containing as an agent which renders the dispersedpolymerized butyl methacrylate substantive to textile fibers a watersoluble salt of a multivalent metal.

11. A substantive textile finishing composition adapted for applicationto textile fibers by a process of exhaustion from a dilute aqueous bathcomprising a stable aqueous dispersion of a polymerized vinylidenecompound containing as the dispersing agent a partially saponifiedpolyvinyl acetate and as an agent which renders the dispersedpolymerized vinyl compound substantive to textile fibers a water solublealuminum salt.

12. A substantive textile finishing composition adapted for applicationto textile fibers by a process of exhaustion from a dilute aqueous bathcomprising a stable aqueous dispersion of a polymerized vinyl acetatecontaining as the dispersing agent a partially saponified polyvinylacetate and as an agent which renders the dispersed polymerized vinylacetate substantive to textile fibers a water soluble aluminum salt.

13. A substantive textile finishing composition adapted for applicationto textile fibers by a proces of exhaustion from a dilute aqueous bathcomprising a stable aqueous dispersion of a polymeriized alkylmethacrylate containing as the dispersing agent a partially saponifle plyvinyl acetate and as an agent which renders the dispersed polymerizedalkyl methacrylate substantive to textile fibers a water solublealuminum salt.

14. A substantive textile finishing composition adapted for applicationto textile fibers by a proc-- ess of exhaustion from a dilute aqueousbath comprising a stable aqueous dispersion of a polymerized methylmethacrylate containing as the dispersing agent a partially saponifledpolyvinyl acetate and as an agent which renders the dispersedpolymerized methyl methacrylate substantive to textile fibers a watersoluble aluminum sal 15. A substantive textile finishing compositionadapted for application to textile fibers by a process of exhaustionfrom a dilute aqueous bath comprising a stable aqueous dispersion of apolymerized butyl methacrylate containing as the dispersing agent apartially saponifled polyvinyl acetate and as an agent which renders thedispersed polymerized butyl methacrylate substantive to textile fibers awater soluble aluminum salt.

JOSEPH EDWARD SMITH.

CERTIFICATE OF commonon.

Patent No. 2,515,089. 7 February 29, 19141;.

JOSEPH EDWARD SMITH.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows: Page I,sec 0nd column, line 19, after "-acetate'i insert --mo reiparticu larlyof the type described in copending application Serial No. 551,082 filedof even date herewith--; and that the said Letters Patent should be readwithv this correction therein that the same may conform to the record ofthe case in the Patent Office.

Signed and sealed this 16th d of ma A. 1). 191m.

Leslie Frazer (Seal) Acting Commissioner of Patents.

